Carbonaceous material for negative electrode active material for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary battery negative electrode, non-aqueous electrolyte secondary battery, and production method of carbonaceous material

ABSTRACT

The present invention provides a carbonaceous material suitable for a negative electrode active material for non-aqueous electrolyte secondary batteries (e.g., lithium ion secondary batteries, sodium ion secondary batteries, lithium sulfur batteries, lithium air batteries) having high charge/discharge capacities, and preferably high charge/discharge efficiency and low resistance, a negative electrode comprising the carbonaceous material, a non-aqueous electrolyte secondary battery comprising the negative electrode, and a production method of the carbonaceous material. The present invention relates to a carbonaceous material having a nitrogen content obtained by elemental analysis of 3.5 mass % or more, a ratio of nitrogen content and hydrogen content (R N/H ) of 6 or more and 100 or less, a ratio of oxygen content and nitrogen content (R O/N ) of 0.1 or more and 1.0 or less, and a carbon interplanar spacing (d 002 ) observed by X-ray diffraction measurement of 3.70 Å or more.

TECHNICAL FIELD

This patent application claims priority under the Paris Convention basedon Japanese Patent Application No. 2017-133034 (filed Jul. 6, 2017)incorporated herein by reference in its entirety.

The present invention relates to a carbonaceous material suitable for anegative electrode active material for non-aqueous electrolyte secondarybatteries, a non-aqueous electrolyte secondary battery negativeelectrode comprising the carbonaceous material, a non-aqueouselectrolyte secondary battery comprising the negative electrode, and aproduction method of carbonaceous material.

BACKGROUND ART

Non-aqueous electrolyte secondary batteries such as lithium ionsecondary batteries have high energy density and excellent outputcharacteristics and are therefore widely used in small portable devicessuch as mobile phones and notebook computers. In recent years, thebatteries are also increasingly applied to in-vehicle use for hybridvehicles, electric vehicles, etc. For a negative electrode material fora lithium ion secondary battery, nitrogen-containing non-graphitizablecarbon capable of being doped (charged) and dedoped (discharged) withlithium in an amount exceeding the theoretical capacity of 372 mAh/g ofgraphite has been developed (e.g., Patent Documents 1, 2, 3) and used.

Nitrogen-containing non-graphitizable carbon can be obtained, forexample, by using a phenol resin as a carbon source and amine as anitrogen source, or using a resin having an amine group such as ananiline resin as a carbon source, and performing a heat treatment.However, when nitrogen-containing non-graphitizable carbon is producedby using these raw materials, a step of fixing the nitrogen element isrequired for increasing a nitrogen element content, which reduces theproductivity, and the fixing step tends to increase oxygen and hydrogenelement contents as well.

The nitrogen element in the carbonaceous material acts as a lithium ionstorage site, has smaller adsorption/desorption energies as compared towhen lithium ions are stored in voids and defect portions between carbonlayers and between carbon crystals, and therefore allows efficient ionicmigration, which tends to lead to lower resistance.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-083012

Patent Document 2: Japanese Patent No. 5233314

Patent Document 3: Japanese Patent No. 5477391

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

Studies are recently conducted on application of lithium ion secondarybatteries to in-vehicle use, and a further increase in capacity oflithium ion secondary batteries is demanded. To further improveinput/output characteristics of non-aqueous electrolyte secondarybatteries, a carbonaceous material providing a battery with low internalresistance may be required.

Therefore, an object of the present invention is to provide acarbonaceous material suitable for a negative electrode active materialfor non-aqueous electrolyte secondary batteries (e.g., lithium ionsecondary batteries, sodium ion secondary batteries, lithium sulfurbatteries, lithium air batteries) having high charge/dischargecapacities, and preferably high charge/discharge efficiency and lowresistance, a negative electrode comprising the carbonaceous material, anon-aqueous electrolyte secondary battery comprising the negativeelectrode, and a production method of the carbonaceous material.

Means for Solving Problem

The present inventors found that the object can be achieved by acarbonaceous material of the present invention described below.

Therefore, the present invention comprises the following preferredaspects.

[1] A carbonaceous material having a nitrogen element content of 3.5mass % or more obtained by elemental analysis, a ratio of nitrogenelement content and hydrogen element content (R_(N/H)) of 6 or more and100 or less, a ratio of oxygen element content and nitrogen elementcontent (R_(O/N)) of 0.1 or more and 1.0 or less, and a carboninterplanar spacing (d₀₀₂) observed by X-ray diffraction measurement of3.70 Å or more.

[2] The carbonaceous material according to [1], wherein a value ofhalf-value width of a peak near 1360 cm⁻¹ and a value of half-valuewidth of a peak near 1650 cm⁻¹ of the Raman spectrum observed by laserRaman spectroscopy exceed 250 cm⁻¹ and 100 cm⁻¹, respectively.

[3] The carbonaceous material according to [1] or [2], wherein aspecific surface area obtained by a BET method is 100 m²/g or more, andwherein a pore volume represented by a sum of a micropore volume and amesopore volume is 0.08 mL/g or more.

[4] The carbonaceous material according to [1] or [2], wherein aspecific surface area obtained by a BET method is 70 m²/g or less, andwherein a pore volume represented by a sum of a micropore volume and amesopore volume is 0.05 mL/g or less.

[5] The carbonaceous material according to any one of [1] to [4],wherein an oxygen element content exceeds 1.5 mass %.

[6] The carbonaceous material according to any one of [1] to [5],wherein the carbonaceous material is derived from a saccharide.

[7] The carbonaceous material according to any one of [1] to [5],wherein the carbonaceous material is for use as a negative electrodeactive material for non-aqueous electrolyte secondary batteries.

[8] A non-aqueous electrolyte secondary battery negative electrodecomprising: the carbonaceous material according to [7].

[9] A non-aqueous electrolyte secondary battery comprising: thenon-aqueous electrolyte secondary battery negative electrode accordingto [8].

[10] A production method of the carbonaceous material according to anyone of [1] to [7], comprising the steps of:

(1) mixing a saccharide with a substance capable of generating ammoniagas;

(2) increasing a temperature of an obtained mixture in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to apredetermined temperature between 500 and 1200° C.; and

(3) applying a heat treatment at a temperature of 500 to 1200° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide to obtain a char.

[11] A production method of the carbonaceous material according to anyone of [1] to [7], comprising the steps of:

(1) mixing a saccharide with a substance capable of generating ammoniagas;

(2A) increasing a temperature of an obtained mixture in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to afirst predetermined temperature between 500 and 1000° C.;

(3A) applying a heat treatment at a temperature of 500 to 1000° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide to obtain a char;

(2B) increasing a temperature of the obtained char in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to asecond predetermined temperature between 800 and 1400° C.; and

(3B) applying a heat treatment at a temperature of 800 to 1400° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thechar.

Effect of the Invention

The non-aqueous electrolyte secondary battery using the negativeelectrode comprising the carbonaceous material of the present inventionhas high charge/discharge capacities and preferably highcharge/discharge efficiency as well as low resistance.

MODES FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will now be described in detail.The scope of the present invention is not limited to the embodiments inthis description, and various modifications can be made withoutdeparting from the spirit of the present invention.

In a carbonaceous material of the present invention, a nitrogen elementcontent obtained by elemental analysis is 3.5 mass % or more. Thenitrogen element content in the carbonaceous material less than 3.5 mass% reduces sites for adsorption/desorption of lithium ions duringcharge/discharge and tends to decrease charge/discharge capacities. Fromthe viewpoint of achieving a sufficient discharge capacity, the nitrogenelement content in the carbonaceous material of the present invention ispreferably 3.55 mass % or more, more preferably 3.65 mass % or more,further preferably 3.75 mass % or more, still further preferably 3.85mass % or more. If the nitrogen element content in the carbonaceousmaterial of the present invention is too large, the carbonaceousmaterial is easily distorted in structure so that a layered structurecannot be maintained, and therefore, the sites for adsorption/desorptionof lithium ions are reduced. Additionally, nitrogen not taken into thecarbon skeleton is expected to exist as a surface functional group suchas —NH₂ group, and if an amount of such a surface functional groupincreases, an irreversible side reaction possibly occurring duringcharge and discharge cannot be suppressed, resulting in a reduction inthe discharge capacity and a reduction in the charge/dischargeefficiency. From the viewpoint of suppressing the irreversible sidereaction during charge and discharge and facilitating increases in thedischarge capacity and the charge/discharge efficiency, the nitrogenelement content in the carbonaceous material of the present invention ispreferably 5.5 mass % or less, more preferably 5.2 mass % or less,further preferably 5.0 mass % or less, still further preferably 4.7 mass% or less, particularly preferably 4.5 mass % or less. Details ofmeasurement of the nitrogen element content are as described later, andthe measurement is performed an elemental analysis method (inert gasdissolution method). A method for adjusting the nitrogen element contentto the range is not limited in any way and, for example, the method cancomprise mixing a saccharide with a substance capable of generatingammonia gas, increasing temperature at 100° C./hour or more in an inertgas atmosphere, and performing a heat treatment at a temperature of 500to 1200° C. with an inert gas flow rate of 0.5 to 5.0 L/min relative to5 g of the saccharide. Particularly, if the inert gas flow rate is madelarger or the temperature increase rate is too small, the nitrogenelement in the carbonaceous material is easily desorbed so that thenitrogen element amount in the obtained carbonaceous material isreduced, and therefore, adjustments may be made in the inert gas flowrate, the temperature increase rate, and the heat treatment temperature.The nitrogen element content within the range also provides an effectthat an impedance value is small after charge and discharge areperformed multiple times (e.g., two, three, five or more times).

In the carbonaceous material of the present invention, a hydrogenelement content obtained by elemental analysis is preferably 0.50 mass %or less, more preferably 0.40 mass % or less, further preferably 0.35mass % or less. The hydrogen element content in the carbonaceousmaterial not more than the upper limit is preferable from the viewpointof reducing a carbon edge portion, expanding a carbon plane, andfacilitating movement of electrons. The hydrogen element content in thecarbonaceous material of the present invention is preferably 0.10 mass %or more, more preferably 0.15 mass % or more, from the viewpoint offacilitating adsorption/desorption of lithium ions. Details ofmeasurement of the hydrogen element content are as described later, andthe measurement is performed by an elemental analysis method (inert gasdissolution method). A method for adjusting the hydrogen element contentto the range is not limited in any way and, for example, the method cancomprise mixing a saccharide with a substance capable of generatingammonia gas, increasing temperature at 100° C./hour or more in an inertgas atmosphere, and performing a heat treatment at a temperature of 500to 1200° C. with an inert gas flow rate of 0.5 to 5.0 L/min relative to5 g of the saccharide.

In the carbonaceous material of the present invention, from theviewpoint of improving an affinity with an electrolytic solution tofacilitate transfer of electrons between the carbonaceous material andthe electrolytic solution and reduce resistance, an oxygen elementcontent obtained by elemental analysis is preferably 0.9 mass % or more,more preferably 1.10 mass % or more, and further preferably more than1.50 mass %. On the other hand, if the oxygen element content is toolarge, an irreversible side reaction possibly occurring during chargeand discharge cannot be suppressed, resulting in a reduction in thedischarge capacity and a reduction in the charge/discharge efficiency.From the viewpoint of suppressing the irreversible side reaction duringcharge and discharge and facilitating increases in the dischargecapacity and the charge/discharge efficiency, the oxygen element contentin the carbonaceous material of the present invention is preferably 3.0mass % or less, more preferably 2.75 mass % or less, further preferably2.50 mass % or less. If higher discharge capacity andcharging/discharging efficiency are required, the oxygen element contentin the carbonaceous material of the present invention not more than 1.5mass % is also preferable. Details of measurement of the oxygen elementcontent are as described later, and the measurement is performed by anelemental analysis method (inert gas dissolution method). A method foradjusting the oxygen element content to the range is not limited in anyway and, for example, the method can comprise mixing a saccharide with asubstance capable of generating ammonia gas, increasing temperature at100° C./hour or more in an inert gas atmosphere, and performing a heattreatment at a temperature of 500 to 1200° C. with an inert gas flowrate of 0.5 to 5.0 L/min relative to 5 g of the saccharide.

In the carbonaceous material of the present invention, a ratio R_(N/H)between the nitrogen element content and the hydrogen element content(nitrogen element content/hydrogen element content) is 6 or more and 100or less, preferably 10 to 80, more preferably 11 to 60, furtherpreferably 12 to 50, from the viewpoint of increasing the nitrogenelement content to facilitate an increase in the discharge capacity. Aratio R_(O/N) between the oxygen element content and the nitrogenelement content (oxygen element content/nitrogen element content) is0.10 to 1.0, preferably 0.15 to 0.90, more preferably from 0.20 to 0.80,further preferably from 0.25 to 0.70, from the viewpoint of increasingboth the oxygen element content and the nitrogen element content tofacilitate a reduction in the resistance. The ratio R_(N/H) between thenitrogen element content and the hydrogen element content is calculatedby an equation R_(N/H)=nitrogen element content/hydrogen element contentfrom the nitrogen element content and the hydrogen element contentmeasured as described above, and the ratio R_(O/N) between the oxygenelement content and the nitrogen element content is calculated from anequation R_(O/N)=oxygen element content/hydrogen element content fromthe oxygen element content and the nitrogen element content measured asdescribed above.

In the carbonaceous material of the present invention, a carboninterplanar spacing (d₀₀₂) calculated by the Bragg equation from a peakposition (diffraction angle 2θ) observed by a powder X-ray diffractionmethod is 3.70 Å or more. For example, when the carbon planes areclosest to each other as in graphite, d₀₀₂ is about 3.35 to 3.40 Å, andif d₀₀₂ exceeds 4.00 Å, the carbon planes cannot interact with eachother and may become unable to maintain a layer structure. From theviewpoint of efficient movement of lithium ions, the carbonaceousmaterial of the present invention preferably has d₀₀₂ widened to adegree not exceeding 4.00 Å. Therefore, a range of d₀₀₂ in thecarbonaceous material of the present invention is usually 3.70 Å to 4.00Å, preferably 3.74 Å to 3.95 Å, more preferably 3.76 Å to 3.90 Å.

In the carbonaceous material of the present invention, a value ofhalf-value width of a peak near 1360 cm⁻¹ of the Raman spectrum observedby laser Raman spectroscopy is preferably in a range exceeding 250 cm⁻¹.The peak near 1360 cm⁻¹ is a Raman peak generally called a D band, whichis a peak attributable to disturbance/defect of the graphite structure.The peak near 1,360 cm⁻¹ is usually observed in a range of 1345 cm⁻¹ to1375 cm⁻¹, preferably 1350 cm⁻¹ to 1370 cm⁻¹. In the carbonaceousmaterial of the present invention, a value of half-value width of a peaknear 1650 cm⁻¹ of the Raman spectrum observed by laser Ramanspectroscopy is preferably in a range exceeding 100 cm⁻¹. The peak near1650 cm⁻¹ is a Raman peak generally called a G band, which is a peakattributable to disturbance/defect of the graphite structure. The peaknear 1,650 cm⁻¹ is usually observed in a range of 90 cm⁻¹ to 120 cm⁻¹,preferably in a range of 100 cm⁻¹ to 110 cm⁻¹.

These half-value widths are related to the amount of disturbance/defectof the graphite structure contained in the carbonaceous material. Suchstructural disturbances may be caused by introduction of the nitrogenelement into the carbon skeleton. If the half-value width of the Ramanpeak in the D band is 250 cm⁻¹ or less, structural developmentexcessively proceeds, and the development of the graphite structuretends to prevent lithium ions from entering and exiting efficiently.This may cause problems such as an increase in resistance. From theviewpoint of facilitating a reduction in resistance, the half-valuewidth of the peak near 1360 cm⁻¹ is preferably in the range exceeding250 cm⁻¹, more preferably 260 m⁻¹ or more, and further preferably 270cm⁻¹ or more. If the half-value width is greater than 300 cm⁻¹, thegraphite structure contained in the carbonaceous material becomesdifficult to maintain, and an amorphous material increases, which tendsto decrease sites that may store lithium. This may cause a reduction instorage amount of lithium ions and a reduction in the dischargecapacity. From such a viewpoint, the half-value width of the peak near1360 cm⁻¹ is preferably 300 cm⁻¹ or less. If the half-value width of theRaman peak in the G band is 100 cm⁻¹ or less, the structural developmentexcessively proceeds, and the development of the graphite structuretends to prevent lithium ions from entering and exiting efficiently.This may cause problems such as an increase in resistance. From theviewpoint of facilitating a reduction in resistance, the half-valuewidth of the peak near 1650 cm⁻¹ is preferably more than 100 cm⁻¹, morepreferably 102 cm⁻¹ or more, further preferably 105 cm⁻¹ or more, andusually 115 cm⁻¹ or less, preferably 110 cm⁻¹ or less, more preferably107 cm⁻¹ or less.

According to the preferred carbonaceous material of the presentinvention having a value of half-value width of the peak near 1360 cm⁻¹of the Raman spectrum observed by laser Raman spectroscopy in the rangeexceeding 250 cm⁻¹ and the hydrogen element content obtained byelemental analysis of 0.50 mass % or less, although the carbon structureis significantly disturbed, a carbon edge portion is relatively small,and therefore, the lithium ion transport efficiency is increased, sothat low resistance and high charge/discharge efficiency are achieved.

The Raman spectrum is measured by using a Raman spectroscope (e.g.,Raman spectroscope “LabRAM ARAMIS (VIS)” manufactured by HORIBA, Ltd.).Specifically, for example, after setting of measurement target particleson an observation stage and focusing an objective lens at magnificationof 100 times, the measurement is performed while applying a 532 nm argonion laser light into a measurement cell with an exposure time of 1second, an accumulation number of 100, and a measurement range of 50 to2000 cm⁻¹.

A method for adjusting the half-value width of the peak near 1360 cm⁻¹and the half-value width of the peak near 1650 cm⁻¹ to the ranges is notlimited in any way and, for example, the method can comprise mixing asaccharide with a substance capable of generating ammonia gas,increasing temperature at 100° C./hour or more in an inert gasatmosphere, and performing a heat treatment at a temperature of 500 to1200° C. with an inert gas flow rate of 0.5 to 5.0 L/min relative to 5 gof the saccharide.

A specific surface area obtained by a nitrogen adsorption BET method ofthe carbonaceous material of the present invention is preferably 100m²/g or more, more preferably 150 m²/g or more, further preferably 200m²/g or more from the viewpoint of facilitating permeation of anelectrolytic solution and facilitating a reduction in batteryresistance. The specific surface area of the carbonaceous material notless than the lower limit also provides an effect that an impedancevalue is small after charge and discharge are performed multiple times(e.g., two, three, five or more times). From the viewpoint of reducingthe hygroscopicity of the carbonaceous material to suppress generationof acid and gas accompanying the hydrolysis of an electrolytic solutionand water due to moisture present in the carbonaceous material and theviewpoint of reducing a contact area between air and the carbonaceousmaterial to suppress oxidation of the carbonaceous material itself, thespecific surface area is preferably 400 m²/g or less, more preferably350 m²/g or less, and further preferably 300 m²/g or less. Details ofmeasurement of the specific surface area by the nitrogen adsorption BETmethod are as described later.

If it is required to further reduce the hygroscopicity of thecarbonaceous material to suppress generation of acid and gasaccompanying the hydrolysis of an electrolytic solution and water due tomoisture present in the carbonaceous material or it is required toreduce a contact area between air and the carbonaceous material tosuppress oxidation of the carbonaceous material itself, the specificsurface area obtained by the nitrogen adsorption BET method of thecarbonaceous material of the present invention is preferably 70 m²/g orless, more preferably 60 m²/g or less, further preferably 40 m²/g orless, still further preferably 30 m²/g or less, and particularlypreferably 20 m²/g or less, most preferably, 12 m²/g or less.

A method for adjusting the specific surface area to the range is notlimited in any way and, for example, the method can comprise mixing asaccharide with a substance capable of generating ammonia gas,increasing temperature at 100° C./hour or more in an inert gasatmosphere, and performing a heat treatment at a temperature of 500 to1200° C. with an inert gas flow rate of 0.5 to 5.0 L/min relative to 5 gof the saccharide.

In the carbonaceous material of the present invention, from theviewpoint of facilitating permeation of an electrolytic solution andfacilitating a reduction in battery resistance, a mesopore volumecalculated by the DFT method is preferably 0.01 mL/g or more, morepreferably 0.02 mL/g or more. The mesopore volume not less than thelower limit is preferable since pore clogging due to a decompositionproduct generated during repeated charge and discharge can be suppressedso that an increase in resistance is easily avoided. From the viewpointof enabling suppression of a bulk density reduction and facilitating anincrease in electrode density, the mesopore volume is preferably 0.07mL/g or less, more preferably 0.06 mL/g or less, further preferably 0.05mL/g or less. In this description, mesopores are pores having a poresize (pore diameter) of 2 nm or more and 50 nm or less in the DFTmethod.

On the other hand, in the carbonaceous material of the presentinvention, if it is required to further suppress a bulk densityreduction to increase the electrode density or it is required tosuppress a side reaction in a charge/discharge process to further reducean irreversible capacity, the mesopore volume calculated by the DFTmethod is preferably 0.02 mL/g or less, more preferably 0.01 mL/g orless.

In the carbonaceous material of the present invention, from theviewpoint of easily causing adsorption/desorption of Li ions, amicropore volume calculated by the DFT method is preferably 0.03 mL/g ormore, more preferably 0.04 mL/G or more, further preferably 0.05 mL/g ormore. From the viewpoint of facilitating suppression of a reactionbetween the carbonaceous material and moisture caused duringcharge/discharge due to moisture adsorption etc., the micropore volumeis preferably 0.15 mL/g or less, preferably 0.12 mL/g or less, furtherpreferably 0.10 mL/g or less. In this description, micropores are poreshaving a pore size (pore diameter) less than 2 nm in the DFT method.

On the other hand, in the carbonaceous material of the presentinvention, if it is required to further suppress the reaction betweenthe carbonaceous material and moisture caused during charge/dischargedue to moisture adsorption etc., the micropore volume calculated by theDFT method is preferably 0.03 mL/g or less, more preferably 0.01 mL/g orless.

The DFT method is an analysis technique using molecular dynamics and acomputer simulation method to calculate an equilibrium density profileof gas adsorbed to a surface and pores of an adsorbed body so thatadsorption/desorption isotherm, adsorption heat, etc. can be calculated.Since this analysis method is applicable to the entire region ofmicropores and mesopores, the micropore volume, the mesopore volume, andthe micropore/mesopore distribution can be measured at the same time. Inthe present invention, the micropore volume and the mesopore volume canbe calculated by applying the DFT method to the nitrogenadsorption/desorption isotherm measured by the nitrogen adsorptionmethod.

In the carbonaceous material of the present invention, regarding a porevolume represented by the sum of the micropore and mesopore volumesrespectively calculated by the method (calculated by the equation ofmesopore volume+micropore volume and hereinafter referred to also as“mesopore volume+micropore volume”), from the viewpoint of obtaining acarbonaceous material suitable for fabricating a battery having a lowinternal resistance, the mesopore volume+micropore volume is preferably0.08 mL/g or more. Although the reason why the above effect can beobtained is not clear, a size of pores likely to be clogged due torepeated charge and discharge depends on types of an electrolyticsolution and a binder to be used and has no fixed rule. Therefore, it isconsidered that a low resistance value is maintained when a certainlevel or more of the micropore volume or the mesopore volume is present.An upper limit of the mesopore volume+micropore volume is 0.30 mL/g orless, for example. The mesopore volume+micropore volume within the rangealso provides an effect that an impedance value is small after chargeand discharge are performed multiple times (e.g., two, three, five ormore times).

A method for adjusting the mesopore volume and the micropore volume aswell as the mesopore volume+micropore volume to the range is not limitedin any way and, for example, the method can comprise mixing a saccharidewith a substance capable of generating ammonia gas, increasingtemperature at 100° C./hour or more in an inert gas atmosphere, andperforming a heat treatment at a temperature of 500 to 1200° C. with aninert gas flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide.

On the other hand, in the carbonaceous material of the presentinvention, from the viewpoint of further reducing an amount of moistureadsorption and suppressing an increase in irreversible capacity, themesopore volume+micropore volume respectively calculated by the methodis 0.07 mL/g or less, more preferably 0.05 mL/g or less, furtherpreferably 0.03 mL/g or less. In this case, a lower limit of themesopore volume+micropore volume is 0.001 mL/g or more, for example.

A method for adjusting the mesopore volume and the micropore volume aswell as the mesopore volume+micropore volume to the range is not limitedin any way and, for example, the method can comprise mixing a saccharidewith a substance capable of generating ammonia gas, increasingtemperature at 100° C./hour or more in an inert gas atmosphere,performing a heat treatment at a first predetermined temperature between500 to 1000° C. with an inert gas flow rate of 0.5 to 5.0 L/min relativeto 5 g of the saccharide, increasing a temperature of an obtained charat 100° C./hour or more in an inert gas atmosphere, performing a heattreatment at a second predetermined temperature between 800 to 1400° C.with an inert gas flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide.

An average particle diameter (D₅₀) of the carbonaceous material of thepresent invention is preferably 2 to 30 μm from the viewpoint ofcoatability during electrode fabrication. The average particle diameternot less than the lower limit is preferable since an increase inspecific surface area and an increase in reactivity with theelectrolytic solution due to fine powder in the carbonaceous materialare suppressed and an increase in irreversible capacity is easilysuppressed. Additionally, when a negative electrode is produced by usingthe obtained carbonaceous material, voids formed in the carbonaceousmaterial can be ensured and the movement of lithium ion in theelectrolytic solution is hardly suppressed. From such a viewpoint, theaverage particle diameter (D₅₀) of the carbonaceous material of thepresent invention is more preferably 3 μm or more, further preferably 4μm or more, particularly preferably 5 μm or more, most preferably 7 μmor more. On the other hand, the average particle diameter not more thanthe upper limit is preferable since a small diffusion free path oflithium ions in the particles facilitates provision of rapid charge anddischarge. Furthermore, in lithium ion secondary batteries, it isimportant to increase an electrode area for improvement of input/outputcharacteristics, and therefore, a coating thickness of an activematerial applied to a collector plate needs to be reduced at the time ofelectrode preparation. To reduce the coating thickness, it is necessaryto reduce the particle diameter of the active material. From such aviewpoint, the average particle diameter is more preferably 20 μm orless, further preferably 18 μm or less, particularly preferably 16 μm orless, most preferably 15 μm or less. D₅₀ is the particle diameter atwhich the cumulative volume is 50% and can be obtained by measuring aparticle size distribution with a laser scattering method using aparticle diameter/particle size distribution measuring device(“Microtrac MT3300EXII” manufactured by MicrotracBEL), for example.

The present invention also provides a production method for acarbonaceous material suitable for a negative electrode active materialor a conductive material for non-aqueous electrolyte secondary batteries(e.g., lithium ion secondary batteries, sodium ion secondary batteries,lithium sulfur batteries, lithium air batteries) having highcharge/discharge capacities and low resistance. The production method isa method comprising the steps of:

(1) mixing a saccharide with a substance capable of generating ammoniagas;

(2) increasing a temperature of an obtained mixture in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to apredetermined temperature between 500 and 1200° C.; and

(3) applying a heat treatment at a temperature of 500 to 1200° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide to obtain a char, and the carbonaceous material of thepresent invention can be obtained by this method. The carbonaceousmaterial can be obtained by a usual method, for example, by pulverizingthe char with a ball mill or a jet mill.

In another embodiment, if it is required to increase the electrodedensity, or it is required to suppress a side reaction in acharge/discharge process to further reduce an irreversible capacity in anegative electrode active material or a conductive material fornon-aqueous electrolyte secondary batteries (e.g., lithium ion secondarybatteries, sodium ion secondary batteries, lithium sulfur batteries,lithium air batteries), the present invention relates to a productionmethod for the carbonaceous material comprising the steps of

(1) mixing a saccharide with a substance capable of generating ammoniagas;

(2A) increasing a temperature of an obtained mixture in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to afirst predetermined temperature between 500 and 1000° C.;

(3A) applying a heat treatment at a temperature of 500 to 1000° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thesaccharide to obtain a char;

(2B) increasing a temperature of the obtained char in an inert gasatmosphere at a temperature increase rate of 100° C./hour or more to asecond predetermined temperature between 800 and 1400° C.; and

(3B) applying a heat treatment at a temperature of 800 to 1400° C. withan inert gas at a flow rate of 0.5 to 5.0 L/min relative to 5 g of thechar.

The saccharide used as a raw material is not particularly limited.Examples thereof comprise monosaccharides such as glucose, galactose,mannose, fructose, ribose, and glucosamine, disaccharides such assucrose, trehalose, maltose, cellobiose, maltitol, lactobionic acid, andlactosamine, and polysaccharides such as starch, glycogen, agarose,pectin, cellulose, chitin, and chitosan. These saccharides can be usedalone or in combination of two or more. Among these saccharides, glucoseis preferable due to easy availability in large amount. By using such asaccharide as a raw material, the carbonaceous material derived from thesaccharide can be obtained.

The substance capable of generating ammonia gas is not particularlylimited and may be any substance capable of generating ammonia gas byheating, and examples of such a substance can comprise inorganicammonium salts such as ammonium chloride, ammonium sulfate, ammoniumcarbonate, and ammonium nitrate, organic ammonium salts such as ammoniumformate, ammonium acetate, ammonium oxalate, and diammonium hydrogencitrate, and aromatic amine hydrochlorides such as aniline hydrochlorideand aminonaphthalene hydrochloride.

A mixing method of the saccharide and the substance capable ofgenerating ammonia gas is not particularly limited, and dry mixing orwet mixing is usable.

In the case of dry mixing, the substance capable of generating ammoniagas can be added to the saccharide to obtain a mixture thereof. In thiscase, from the viewpoint of uniformly mixing the substance capable ofgenerating ammonia gas and the saccharide, for example, the substancecapable of generating ammonia gas and the saccharide are preferablypowdered and mixed while being ground down with a mortar or pulverizedwith a ball mill.

In the case of wet mixing, for example, the saccharide can be dissolvedin a solvent to prepare a solution, and the substance capable ofgenerating ammonia gas can then be added to and mixed with the solution.The mixing may be achieved by scattering (spraying etc.) of the solutionto the substance capable of generating ammonia gas. Alternatively, thesaccharide may be added to and mixed with a solution prepared bydissolving the substance capable of generating ammonia gas in a solvent.After the mixing, the solvent may be evaporated if necessary. By such atreatment, a mixture of the saccharide and the substance capable ofgenerating ammonia gas can be obtained. The solvent to be used is notparticularly limited, and examples thereof comprise water, alcoholsolvents (ethanol, methanol, ethylene glycol, isopropyl alcohol, etc.),ester solvents (ethyl acetate, butyl acetate, ethyl lactate, etc.),ether solvents (tetrahydrofuran, dimethoxyethane, 1, 4-dioxane, etc.),ketone solvents (acetone, 2-butanone, cyclopentanone, cyclohexanone,etc.), aliphatic hydrocarbon solvents (pentane, hexane, heptane, etc.),aromatic hydrocarbon solvents (toluene, xylene, mesitylene, etc.),nitrile solvents (acetonitrile, etc.), and chlorinated hydrocarbonsolvents (dichloromethane, chloroform, chlorobenzene, etc.), andmixtures thereof. Uniform mixing of the saccharide and the substancecapable of generating ammonia gas is effectively achieved when both areeasily dissolved in the solvent, and therefore, water, an alcoholsolvent, and a mixture thereof are preferable as the solvent. A methodof evaporating the solvent is not particularly limited and, examplethereof comprise a heat treatment and a pressure reduction treatment aswell as a method of applying a combination thereof. The temperature ofthe heat treatment may be a temperature hardly causing the pyrolysis ofthe substance capable of generating ammonia gas or a temperature hardlycausing the pyrolysis of the saccharide and is preferably 40 to 150° C.,more preferably 50 to 120° C., further preferably 60 to 100° C.,although varying depending on a type of the solvent.

An amount (addition amount) of the substance capable of generatingammonia gas to be mixed with the saccharide is preferably 0.5 molarequivalent or more, more preferably 0.7 molar equivalent or more,further preferably 0.9 molar equivalent or more, particularly preferably1.0 molar equivalent or more, and preferably 5.0 molar equivalent orless, more preferably 4.0 molar equivalent or less, further preferably3.5 molar equivalent or less. The amount of the substance capable ofgenerating ammonia gas to be mixed is preferably not less than the lowerlimit since the nitrogen element is efficiently taken into the obtainedcarbonaceous material. When the amount of the substance capable ofgenerating the ammonia gas to be mixed is not more than the upper limit,the nitrogen element can be prevented from being excessively taken in,and therefore, the carbon structure is not excessively disturbed, sothat an non-aqueous electrolyte secondary battery comprising theobtained carbonaceous material exhibits high charge/discharge capacitiesand is also facilitated to exhibit a low resistance.

In the production method of the present invention, the mixture obtainedfrom step (1) of mixing a saccharide with a substance capable ofgenerating ammonia gas is increased in temperature and calcined [step(2) and step (3)] to obtain a char. Suitably, the mixture obtained fromstep (1) is increased in temperature and is subjected to a heattreatment at a temperature between 500 and 1200° C., preferably 600 and1150° C., more preferably 700 and 1100° C., further preferably 800 and1100° C. with an inert gas at a flow rate of 0.5 to 5.0 L/min,preferably a flow rate of 0.6 to 4.0 L/min, more preferably a flow rateof 0.7 to 3.0 L/min, relative to 5 g of the saccharide to obtain a char[step (3)]. An example of the inert gas is nitrogen gas. The temperatureof the heat treatment applied with the inert gas may be a constanttemperature and is not particularly limited as long as the temperatureis within the range.

In this case, the mixture obtained from step (1) of mixing a saccharidewith a substance capable of generating ammonia gas is suitably increasedin temperature in an inert gas atmosphere such as nitrogen gas at atemperature increase rate of 100° C./hour or more, preferably 100 to350° C./hour, more preferably 130 to 320° C./hour, further preferably150 to 300° C./hour to a predetermined temperature between 500 and 1200°C., preferably 600 and 1150° C., more preferably 700 and 1100° C.,further preferably 800 and 1100° C. [step (2)]. The temperature isincreased at step (2) in an inert gas atmosphere, and the heat treatmentmay be applied with an inert gas at a flow rate of 0.5 to 5.0 L/min,preferably a flow rate of 0.6 to 4.0 L/min, more preferably a flow rateof 0.7 to 3.0 L/min, relative to 5 g of the saccharide.

The calcining step, i.e., a combination of the temperature increase stepand the heat treatment step may be repeated multiple times, and when thestep is repeated twice, suitably, at a temperature of 500 to 1000° C.,preferably 520 to 950° C., more preferably 540 to 900° C., furtherpreferably 560 to 850° C. at step (2A), the heat treatment is appliedwith an inert gas at a flow rate of 0.5 to 5.0 L/min, preferably a flowrate of 0.6 to 4.0 L/min, more preferably a flow rate of 0.7 to 3.0L/min, relative to 5 g of the saccharide to obtain a char [step (3A)],and subsequently, at a temperature of 800 to 1400° C., preferably 840 to1300° C., more preferably 880 to 1200° C., further preferably 920 to1100° C. at step (2B), the heat treatment is applied with an inert gasat a flow rate of 0.5 to 5.0 L/min, preferably a flow rate of 0.6 to 4.0L/min, more preferably a flow rate of 0.7 to 3.0 L/min, relative to 5 gof the saccharide to obtain a char [step (3B)].

The carbonaceous material of the present invention or the carbonaceousmaterial obtained by the production method of the present invention cansuitably be used as a negative electrode active material for non-aqueouselectrolyte secondary batteries. The present invention also provides anon-aqueous electrolyte secondary battery negative electrode comprisingthe carbonaceous material of the present invention.

A production method of the non-aqueous electrolyte secondary batterynegative electrode of the present invention will hereinafterspecifically be described. The negative electrode of the presentinvention can be produced by adding a binder to the carbonaceousmaterial of the present invention, adding an appropriate amount of asuitable solvent, kneading the material into an electrode mixture, thenapplying and drying the mixture on a collector plate made up of a metalplate etc., and performing pressure forming.

By using the carbonaceous material of the present invention, ahighly-conductive electrode (negative electrode) can be produced withoutadding a conductive assistant. For the purpose of imparting higherconductivity, a conductive assistant can be added at the time ofpreparation of the electrode mixture as needed. Conductive carbon black,vapor-grown carbon fibers (VGCF), nanotube, etc. can be used as theconductive assistant. Although an addition amount of the conductiveassistant varies depending on a type of the conductive assistant to beused, the expected conductivity may not be obtained if the additionamount is too small, and the dispersion in the electrode mixture may bepoor if the amount is too large. From such a viewpoint, a preferableproportion of the conductive assistant to be added is 0.5 to 10 mass %(assuming the amount of the active material (carbonaceous material)+theamount of the binder+the amount of the conductive assistant=100 mass %),more preferably 0.5 to 7 mass %, particularly preferably 0.5 to 5 mass%. The binder may be any binder not reactive with an electrolyticsolution, such as PVDF (polyvinylidene fluoride),polytetrafluoroethylene, and a mixture of SBR (styrene-butadiene rubber)and CMC (carboxymethyl cellulose), without particular limitation. Amongothers, PVDF is preferable since PVDF having adhered to the surface ofthe active material is less likely to inhibit the lithium ion migrationso that favorable input/output characteristics are obtained. Although apolar solvent such as N-methylpyrrolidone (NMP) is preferably used fordissolving the PVDF and forming a slurry, an aqueous emulsion such asSBR or CMC dissolved in water is also usable. If the addition amount ofthe binder is too large, the resistance of the obtained electrodebecomes large, so that an increased internal resistance of the batterymay deteriorate the battery characteristics. If the addition amount ofthe binder is too small, bonding between the particles of the negativeelectrode material and with the collector plate may be insufficient.Although a preferable addition amount of the binder varies depending ona type of the binder to be used, for example, the addition amount of thePVDF-based binder is preferably 3 to 13 mass %, more preferably 3 to 10mass %. On the other hand, when water is used as a solvent of thebinder, a plurality of binders is often mixed and used as in the case ofa mixture of SBR and CMC, and the total amount of all the binders to beused is preferably 0.5 to 5 mass %, more preferably 1 to 4 mass %. Thecarbonaceous material of the present invention in the electrode mixtureis preferably 80 mass % or more, more preferably 90 mass % or more. Thecarbonaceous material of the present invention in the electrode mixtureis preferably 100 mass % or less, and more preferably 97 mass % or less.

An electrode active material layer is basically formed on both sides ofthe collector plate or may be formed on one side as necessary. Thethicker electrode active material layer is preferable for highercapacity since the collector plate, a separator, etc. can be reduced.However, a wider electrode area opposed to a counter electrode is moreadvantageous for improvement of input/output characteristics, andtherefore, when the electrode active material layer is too thick, theinput/output characteristics may deteriorate. From the viewpoint ofoutput during battery discharge, a thickness of the active materiallayer (per one side) is preferably 10 to 80 μm, more preferably 20 to 75μm, further preferably 30 to 75 μm.

A non-aqueous electrolyte secondary battery of the present inventioncomprises the non-aqueous electrolyte secondary battery negativeelectrode of the present invention. The non-aqueous electrolytesecondary battery having the non-aqueous electrolyte secondary batterynegative electrode comprising the carbonaceous material of the presentinvention has high charge/discharge capacities and charge/dischargeefficiency as well as a low resistance.

When the negative electrode for a non-aqueous electrolyte secondarybattery is formed by using the carbonaceous material of the presentinvention, various materials conventionally used or proposed fornon-aqueous electrolyte secondary batteries can be used for othermaterials constituting the battery, such as a positive electrodematerial, the separator, and the electrolytic solution, withoutparticular limitation.

For example, for the positive electrode material, layered oxide-based(represented by LiMO₂, where M is metal: e.g., LiCoO₂, LiNiO₂, LiMnO₂,or LiNi_(x)Co_(y)Mo_(z)O₂ (x, y, and z represent composition ratios)),olivine-based (represented by LiMPO₄, where M is metal: e.g., LiFePO₄),and spinel-based (represented by LiM₂O₄, where M is metal: e.g.,LiMn₂O₄) composite metal chalcogen compounds are preferable, and thesechalcogen compounds may be mixed as needed. The positive electrode isformed by shaping these positive electrode materials together with asuitable binder and a carbonaceous material for imparting conductivityto an electrode such that a layer is formed on the conductive collectorplate.

A non-aqueous solvent type electrolyte solution used in combination withthese positive and negative electrodes is generally formed by dissolvingan electrolyte in a non-aqueous solvent. For the non-aqueous solvent,for example, one or more organic solvents such as propylene carbonate,ethylene carbonate, dimethyl carbonate, diethyl carbonate,dimethoxyethane, diethoxyethane, γ-butyrolactone, tetrahydrofuran,2-methyltetrahydrofuran, sulfolane, or 1,3-dioxolane can be used aloneor in combination. For the electrolyte, LiClO₄, LiPF₆, LiBF₄, LiCF₃SO₃,LiAsF₆, LiCl, LiBr, LiB(C₆H₅)₄, or LiN(SO₃CF₃)₂ is used.

The non-aqueous electrolyte secondary battery is generally formed byimmersing in the electrolytic solution the positive electrode and thenegative electrode formed as described above and opposed to each otheracross a separator as needed. For such a separator, a permeable orliquid-permeable separator made of nonwoven fabric normally used for asecondary battery or other porous materials can be used. Alternatively,a solid electrolyte made of polymer gel impregnated with an electrolyticsolution may be used instead of, or together with, the separator.

The carbonaceous material of the present invention is suitable for acarbonaceous material for a battery (typically, a non-aqueouselectrolyte secondary battery for driving a vehicle) mounted on avehicle such as an automobile. In the present invention, the vehiclerefers to a vehicle generally known as an electric vehicle, a hybridvehicle with a fuel cell and an internal combustion engine, etc. withoutparticular limitation; however, the vehicle at least comprises a powersource device provided with the battery, an electric drive mechanismdriven by power supply from the power source device, and a controldevice controlling this mechanism. The vehicle may further comprise amechanism provided with a power generation brake and a regenerativebrake and converting energy from braking into electricity to charge thenon-aqueous electrolyte secondary battery.

The carbonaceous material of the present invention has low resistanceand therefore can also be used as an additive imparting conductivity toelectrode materials for batteries, for example. Although the types ofthe batteries are not particularly limited, non-aqueous electrolytesecondary batteries and lead storage batteries are suitable. Thecarbonaceous material added to an electrode material of such a batterycan form a conductive network, and a resulting increase in conductivityenables suppression of an irreversible reaction, so that the battery canhave a longer service life.

EXAMPLES

The present invention will hereinafter specifically be described withexamples; however, the present invention is not limited to theseexamples. A method for measuring physical property values of thecarbonaceous material will hereinafter be described, and the physicalproperty values described in this description comprising the examplesare based on values obtained by the following methods.

(Elemental Analysis)

Elemental analysis was performed by using the oxygen/nitrogen/hydrogenanalyzer EMGA-930 manufactured by HORIBA, Ltd.

The detection methods of the analyzer are oxygen: inert gasfusion-non-dispersive infrared absorption method (NDIR), nitrogen: inertgas fusion-thermal conductivity method (TCD), and hydrogen: inert gasfusion-non-dispersive infrared absorption method (NDIR) calibrated withan (oxygen/nitrogen) Ni capsule, TiH₂ (H standard sample), and SS-3 (N,O standard sample), and 20 mg of a sample having moisture contentmeasured at 250° C. for about 10 minutes for a pretreatment was put intoan Ni capsule and measured after 30 seconds of degasification in theelemental analyzer. The test was performed by analyzing three specimens,and an average value was used as an analysis value.

(X-Ray Diffraction)

X-ray diffraction measurement was performed by filling a carbonaceousmaterial powder in a sample holder and using MiniFlex II manufactured byRigaku Corporation. CuKα (λ=1.5418 Å) was used as a radiation source,and the scanning range was 10°<2θ<35°.

(Raman Spectrum)

Measurement was performed by using the Raman spectroscope (“LabRAMARAMIS (VIS)” manufactured by HORIBA, Ltd.) with measurement targetparticles of carbonaceous material set on an observation stage and anobjective lens focused at magnification of 100 times while applying anargon ion laser light. Details of measurement conditions are as follows.

Argon ion laser light wavelength: 532 nmLaser power on sample: 15 mWResolution: 5 to 7 cm⁻¹Measurement range: 50 to 2000 cm⁻¹Exposure time: 1 secondAccumulation number: 100Peak intensity measurement:

Baseline correction, automatic correction with Polynom/third-order

Peak search and fitting process, GaussLoren

(Specific Surface Area by Nitrogen Adsorption BET Method)

An approximate equation derived from a BET equation is described below.

$\begin{matrix}{\frac{p\text{/}p_{0}}{v\left( {1 - {p\text{/}p_{0}}} \right)} = {\frac{1}{v_{m}c} + \frac{\left( {c - 1} \right)p}{v_{m}c\mspace{14mu} p_{0}}}} & \left\lbrack {{Mathematical}\mspace{14mu} 1} \right\rbrack\end{matrix}$

By using the approximate equation, v_(m) is obtained by substituting anactually measured adsorption amount (v) at a predetermined relativepressure (p/p₀) by a multi-point method according to nitrogen adsorptionat the liquid nitrogen temperature, and the specific surface area (SSA:in m² g⁻¹) of the sample was calculated by the following equation.

$\begin{matrix}{{{specific}\mspace{14mu} {surface}\mspace{14mu} {area}} = {\left( \frac{v_{m}{Na}}{22400} \right) \times 10^{- 18}}} & \left\lbrack {{Mathematical}\mspace{14mu} 2} \right\rbrack\end{matrix}$

In the equation, v_(m) is the adsorption amount (cm³/g) required forforming a monomolecular layer on a sample surface, v is the actuallymeasured adsorption amount (cm³/g), p₀ is the saturated vapor pressure,p is the absolute pressure, c is the constant (reflecting the adsorptionheat), N is the Avogadro's number 6.022×10²³, and a (nm²) is the areaoccupied by adsorbate molecules on the sample surface (molecularoccupied cross-sectional area).

Specifically, the amount of nitrogen adsorption to the carbonaceousmaterial at the liquid nitrogen temperature was measured by using“Autosorb-iQ-MP” manufactured by Quantachrome as follows. After thecarbonaceous material used as a measurement sample was filled in asample tube and the sample tube was cooled to −196° C., the pressure wasonce reduced, and nitrogen (purity: 99.999%) was then adsorbed to themeasurement sample at a desired relative pressure. An adsorbed gasamount v was defined as an amount of nitrogen adsorbed to the samplewhen the equilibrium pressure was reached at each desired relativepressure.

The adsorption isotherm obtained from the measurement of the nitrogenadsorption amount was analyzed by the DFT method, and a volume of poreshaving a pore size (pore diameter) less than 2 nm and a volume of poreshaving a pore size (pore diameter) of 2 nm or more and 50 nm or less arecalculated as the micropore volume and the mesopore volume,respectively.

(Average Particle Diameter by Laser Scattering Method)

The average particle diameter (particle size distribution) ofplant-derived char and the carbonaceous material was measured by thefollowing method. The sample was put into an aqueous solution containing5 mass % surfactant (“Toriton X100” manufactured by Wako Pure ChemicalIndustries), treated by an ultrasonic cleaner for 10 minutes or more,and dispersed in the aqueous solution. The particle size distributionwas measured by using this dispersion. Particle size distributionmeasurement was performed by using a particle diameter/particle sizedistribution measuring device (“Microtrac MT3000EXII” manufactured byMicrotracBEL). D₅₀ is the particle diameter at which the cumulativevolume is 50%, and this value was used as the average particle diameter.

Example 1

Glucose and ammonium chloride (1.1 mol per 1 mol of glucose) were mixedin a mortar. An obtained mixture was increased in temperature to 1000°C. in a nitrogen gas atmosphere. In this process, the temperatureincrease rate to 1000° C. was 240° C./hour (4° C./min). The mixture wasthen heat-treated at 1000° C. for 60 minutes under a nitrogen gas streamto perform a carbonization treatment and thereby obtain a char. In thisprocess, a supply amount of nitrogen gas was 1 L/min per 5 g of glucose.Subsequently, the char was pulverized by a ball mill to obtain acarbonaceous material.

Example 2

A carbonaceous material was obtained by performing the treatments as inExample 1 except that ammonium sulfate was used instead of ammoniumchloride.

Example 3

A carbonaceous material was obtained by performing the treatments as inExample 1 except that the addition amount of ammonium chloride was 0.33mol per 1 mol of glucose.

Example 4

A carbonaceous material was obtained by performing the treatments as inExample 1 except that the addition amount of ammonium chloride was 3.3mol per 1 mol of glucose.

Example 5

A carbonaceous material was obtained by performing the treatments as inExample 1 except that starch was used instead of glucose and diammoniumhydrogen citrate was used instead of ammonium chloride (1.1 mol per 1mol of monosaccharide unit of starch), that before the step ofincreasing the temperature of the obtained mixture to 1000° C. in anitrogen gas atmosphere, the obtained mixture was increased intemperature to 600° C. in a nitrogen gas atmosphere with the temperatureincrease rate to 600° C. set to 240° C./hour (4° C./min), that themixture was then heat-treated at 600° C. for 60 minutes under a nitrogengas stream to perform a carbonization treatment and thereby obtain achar, and that the obtained char was subjected to the temperatureincrease step and the heat treatment step as in Example 1.

Example 6

A carbonaceous material was obtained by performing the treatments as inExample 5 except that the addition amount of diammonium hydrogen citrateused was 0.55 mol per 1 mol of monosaccharide unit of starch.

Comparative Example 1

A carbonaceous material was obtained as in Example 1 except thatammonium chloride was not mixed.

Comparative Example 2

A carbonaceous material was obtained by performing the treatments as inComparative Example 1 except that coconut shell was used as the carbonsource.

Comparative Example 3

A carbonaceous material was obtained by performing the treatments as inExample 1 except that coconut shell was used as the carbon source andammonium chloride (36 mass % relative to the coconut shell) was mixed.

Comparative Example 4

A carbonaceous material was obtained by performing the treatments as inExample 1 except that the nitrogen gas supply amount during thecarbonization treatment was 10 L/min per 5 g of glucose.

Comparative Example 5

In a three-necked flask equipped with a stirrer and a cooling tube, 100parts of aniline, 697 parts of 37% formaldehyde aqueous solution, and 2parts of oxalic acid were placed, reacted at 100° C. for 3 hours, anddehydrated to obtain 110 parts of aniline resin. The obtained anilineresin had a weight average molecular weight of about 700. A resincomposition obtained by pulverizing and mixing 100 parts of the anilineresin obtained as described above and 10 parts of hexamethylenetetramineis treated in the order of the following steps (1) to (4) to obtain acarbonaceous material.

(1) Without performing reducing gas replacement, inert gas replacement,reducing gas circulation, or inert gas circulation, the composition wasincreased in temperature to 500° C. at a temperature increase time of100° C./hour (1.7° C./min), subjected to a degreasing treatment at 500°C. for 2 hours, and then cooled to obtain a char.

(2) The char was pulverized with a ball mill to obtain a pulverizedchar.

(3) The temperature was increased to 1100° C. with a nitrogen gas supplyamount of 3 L/min per 5 g of the pulverized char at a temperatureincrease rate of 100° C./hour (1.7° C./min) and then kept for 8 hours.

(4) The pulverized char was cooled to room temperature with a nitrogengas supply amount of 3 L/min per 5 g of the pulverized char to obtain acarbonaceous material.

(Production of Electrode)

By using the carbonaceous materials obtained in Examples and ComparativeExamples, respective negative electrodes were fabricated according tothe following procedure.

A slurry was obtained by mixing 92 parts by mass of the carbonaceousmaterial, 4 parts by mass of PVDF (polyvinylidene fluoride), and 90parts by mass of NMP (N-methylpyrrolidone). The obtained slurry wasapplied to a copper foil having a thickness of 14 μm, dried, and thenpressed to obtain an electrode having a thickness of 75 μm. The obtainedelectrode had a density of 0.8 to 1.0 g/cm³.

(Impedance)

To the fabricated electrode, an amplitude of 10 mV was applied with 0 Vdefined as the center at 25° C. by using an electrochemical measurementdevice (“1255WB high-performance electrochemical measurement system”manufactured by Solartron) to measure a constant voltage AC impedance ata frequency of 10 mHz to 1 MHz, and real part resistance at frequenciesof 1 kHz, 1 Hz, and 0.1 Hz was measured as impedance resistance.

(DC Resistance Value, Battery Initial Capacity, and Charge/DischargeEfficiency)

The electrode fabricated as described above was used as a workingelectrode, and metallic lithium was used as a counter electrode and areference electrode. Propylene carbonate and ethylene glycol dimethylether were mixed and used as a solvent at a volume ratio of 1:1. In thissolvent, 1 mol/L of LiClO₄ was dissolved and used as an electrolyte. Apolypropylene film was used for the separator. A coin cell wasfabricated in a glove box under an argon atmosphere.

For the lithium secondary battery having the structure described above,a charge/discharge test was performed after measuring DC resistancevalue before initial charge by using a charge/discharge test device(“TOSCAT” manufactured by Toyo System). Doping of lithium was performedat a rate of 70 mA/g with respect to the active material mass, anddoping was performed to 1 mV relative to the lithium potential. Aconstant voltage of 1 mV relative to the lithium potential was furtherapplied for 8 hours before terminating the doping. A capacity (mAh/g) atthis point was defined as the charge capacity. Subsequently, dedopingwas performed at a rate of 70 mA/g with respect to the active materialmass to 2.5 V relative to the lithium potential, and a capacitydischarged at this point was defined as the discharge capacity. Thepercentage of the discharge capacity/charge capacity was defined as thecharge/discharge efficiency (initial charge/discharge efficiency) andwas used as an index of the utilization efficiency of lithium ions inthe battery. After the charge/discharge described above was repeatedthree times, the impedance was measured.

The carbonaceous material production conditions in Examples andComparative Examples, the evaluation results of the physical propertiesof the obtained carbonaceous materials, and the evaluation results ofthe battery characteristics are respectively described in the followingtables.

The battery fabricated by using the carbonaceous materials of Exampleshad a low resistance value and exhibited a high discharge capacity.Particularly, it was found that the impedance value was small after thecharge/discharge measurement was performed three times. The batteriesfabricated by using the carbonaceous materials of Examples 5 and 6 had aremarkable effect of reducing an irreversible capacity as compared toComparative Examples and had high charging/discharging efficiency. Onthe other hand, in the case of the batteries fabricated by using thecarbonaceous materials of Comparative Examples without R_(N/H) orR_(O/N) in a predetermined range or without a predetermined nitrogencontent, a sufficiently low resistance value was not achieved, and thedischarge capacity was not sufficient.

TABLE 1 carbonaceous material manufacturing conditions temperatureincrease N₂ flow calcining rate during rate during raw material mixingratio temperature calcining calcining type No. carbon source ammoniumsalt mol ratio ° C. ° C./min L/min Example 1 glucose NH₄Cl 1:1.1 1000 41 2 glucose (NH₄)₂SO₄ 1:1.1 1000 4 1 3 glucose NH₄Cl  1:0.33 1000 4 1 4glucose NH₄Cl 1:3.3 1000 4 1 5 starch diammonium 1:1.1 1000 4 1 hydrogencitrate 6 starch diammonium  1:0.55 1000 4 1 hydrogen citrateComparative 1 glucose none none 1000 4 1 Example 2 coconut shell nonenone 1000 4 1 3 coconut shell NH₄Cl  1:0.36 1000 4 1 (mass ratio) 4glucose NH₄Cl 1:1.1 1000 4 10 5 aniline resin:formaldehyde:oxalic acid100:697:2 1100 1.7 3

TABLE 2 carbonaceous material physical properties X-ray diffractionRaman spectrum d₀₀₂ D-band G-band R value type No. Å cm⁻¹ cm⁻¹I_(D)/I_(G) Example 1 3.80 283 102 1.17 2 3.82 294 108 1.28 3 3.80 254100 1.17 4 3.75 288 103 1.21 5 3.75 288 103 1.21 6 3.80 276 102 1.18Comparative 1 3.92 219 96 1.18 Example 2 3.79 246 97 1.08 3 3.77 264 991.12 4 3.89 244 97 1.16 5 3.66 165 97 1.12

TABLE 3 carbonaceous material physical properties N₂ adsorptionmeasurement SSA micropore mesopore type No. m²g⁻¹ mLg⁻¹ mLg⁻¹ Example 1260.7 0.0930 0.0612 2 203.4 0.0975 0.0379 3 116.3 0.0442 0.142 4 180.20.0640 0.0284 5 5.9 0.0009 0.0121 6 9.1 0.0014 0.0061 Comparative 1117.3 0.0416 0.0210 Example 2 45.2 0.0071 0.0172 3 39.1 0.0052 0.0180 472.5 0.0092 0.0234 5 7.1 0.0015 0.0037

TABLE 4 carbonaceous material physical properties elemental analysis O NH type No. mass % mass % mass % N/H ratio O/N ratio Example 1 1.90 4.480.31 14.62 0.42 2 1.76 4.81 0.23 21.10 0.37 3 2.53 3.84 0.33 11.57 0.664 2.64 5.17 0.30 17.15 0.51 5 1.12 4.48 0.27 16.59 0.25 6 1.39 4.43 0.2716.41 0.31 Comparative 1 1.23 0.63 0.37 1.71 1.95 Example 2 1.91 1.140.54 2.09 1.68 3 2.39 2.09 0.49 4.24 1.14 4 1.21 0.92 0.25 3.68 1.32 51.55 2.90 0.55 5.3 0.53

TABLE 5 carbonaceous material battery characteristics charge/dischargecharacteristics discharge irreversible capacity capacity efficiency typeNo. mAhg⁻¹ mAhg⁻¹ % Example 1 516 270 65.7 2 506 304 62.5 3 447 282 61.34 508 281 64.4 5 533 208 71.9 6 546 198 73.4 Comparative 1 460 273 62.8Example 2 361 261 58.0 3 410 291 58.5 4 405 242 62.6 5 412 237 63.5

TABLE 6 carbonaceous material battery characteristics charge/dischargecharacteristics DC resistance impedance during during impedance initialinitial (after charging/ charge/ charge/ discharging 3 times) dischargedischarge 1 kHz 1 Hz 0.1 Hz type No. Ω Ω Ω Ω Ω Example 1 410 9.1 5.0 6.27.1 2 401 9.7 4.9 6.0 7.0 3 500 9.9 5.2 6.1 7.2 4 405 9.3 4.9 6.0 7.3 5658 10.8 5.0 6.1 7.2 6 693 10.9 5.3 6.3 7.2 Comparative 1 514 9.7 5.36.9 9.8 Example 2 1037 12 6.9 9.2 11.2 3 1098 11 7.0 9.1 10.2 4 595 9.75.7 6.6 9.9 5 720 10.4 6.2 9.5 11.2

1. A carbonaceous material having a nitrogen content of 3.5 mass % ormore as measured by elemental analysis, a ratio of the nitrogen contentand a hydrogen content (R_(N/H)) of 6 or more and 100 or less, a ratioof an oxygen content and the nitrogen content (R_(O/N)) of 0.1 or moreand 1.0 or less, and a carbon interplanar spacing (d₀₀₂) observed byX-ray diffraction measurement of 3.70 Å or more.
 2. The carbonaceousmaterial according to claim 1, wherein a value of half-value width of apeak near 1360 cm⁻¹ and a value of half-value width of a peak near 1650cm⁻¹ of a Raman spectrum observed by laser Raman spectroscopy exceed 250cm⁻¹ and 100 cm⁻¹, respectively.
 3. The carbonaceous material accordingto claim 1, wherein a specific surface area measured by a BET method is100 m²/g or more, and wherein a pore volume represented by a sum of amicropore volume and a mesopore volume is 0.08 mL/g or more.
 4. Thecarbonaceous material according to claim 1, wherein a specific surfacearea measured by a BET method is 70 m²/g or less, and wherein a porevolume represented by a sum of a micropore volume and a mesopore volumeis 0.05 mL/g or less.
 5. The carbonaceous material according to claim 1,wherein the oxygen content exceeds 1.5 mass %.
 6. The carbonaceousmaterial according to claim 1, wherein the carbonaceous material isderived from a saccharide.
 7. A negative electrode active material for anon-aqueous electrolyte secondary battery, wherein the negativeelectrode active material comprises the carbonaceous material accordingto claim
 1. 8. A non-aqueous electrolyte secondary battery negativeelectrode comprising the carbonaceous material according to claim
 7. 9.A non-aqueous electrolyte secondary battery comprising the non-aqueouselectrolyte secondary battery negative electrode according to claim 8.10. A method of producing carbonaceous material according to claim 1,the method comprising: (1) mixing a saccharide with a substance capableof generating ammonia gas to obtain a mixture; (2) increasing atemperature of the mixture in an inert gas atmosphere at a temperatureincrease rate of 100° C./hour or more to a predetermined temperaturebetween 500 and 1200° C.; and (3) applying a heat treatment at atemperature of 500 to 1200° C. with an inert gas at a flow rate of 0.5to 5.0 L/min relative to 5 g of the saccharide to obtain a char.
 11. Amethod of producing the carbonaceous material according to claim 1, themethod comprising: (1) mixing a saccharide with a substance capable ofgenerating ammonia gas to obtain a mixture; (2A) increasing atemperature of the mixture in an inert gas atmosphere at a temperatureincrease rate of 100° C./hour or more to a first predeterminedtemperature between 500 and 1000° C.; (3A) applying a heat treatment ata temperature of 500 to 1000° C. with an inert gas at a flow rate of 0.5to 5.0 L/min relative to 5 g of the saccharide to obtain a char; (2B)increasing a temperature of the char in an inert gas atmosphere at atemperature increase rate of 100° C./hour or more to a secondpredetermined temperature between 800 and 1400° C.; and (3B) applying aheat treatment at a temperature of 800 to 1400° C. with an inert gas ata flow rate of 0.5 to 5.0 L/min relative to 5 g of the char.